Method of treating radio-active barium compounds.



UNITED STATES PATENT OFFICE.

HERBERT N. MCCOY, OF CHICAGO, ILLINOIS.

METHOD- OF TREATING RADIO-ACTIVE BARIUM COMPOUNDS.

No Drawing.

active substances for the purpose of separating or concentrating the radioactive,

bodies therein. A

I have discovered that radium hydroxid is more soluble in coldiwater,"as well 'as'in cold vsolutions of caustic alkalis, than is barium hydroxid and may, therefore, under proper conditions, be concentrated in solution by fractional recrystallization or frac-' tional precipitation of the mixed hydroxids. This may be accomplished either by concentreating the solutions containing the mixed hydroxids, with proper cooling, in such manner as to secure a fractional recrystallization; or-it'may be accomplished by adding tothe aqueous solution of the mixed bydroxids a. precipitant for such hydroxids, preferably a strong solution of caustic soda or caustic potash. The radio-active sub stances, mesothorium-one and thorium-X behave chemically like radium and may be concentrated in like manner;

It is well known that radium is very similar in its chemical properties to barium; and the best, method heretofore known for effecting .a separation of the two elements, or a concentration of the radium-content of the barium, depends upon a long series of fractional crystallizations of certain salts.

notably the chlorids or bromids. When the mixed chlorids are fractionally crystallized from water, if one-half of the salt is permitted' to crystallize out, it is found to contain about 65 per cent. of the radium, or,

in other words, 1.3 per cent. of the radium,

for each one per cent. of the barium in the original chlorids. On the ot-her hand, the concentration of the hydroxide by fractional crystallization, as hereinafter described according to method I, permits theseparation of about 35 per cent. of, the radium with five per cent; of the barium, or seven per cent. of the rad um for each one Specification of Letters Patent.

Patented July 14., 1914.

Application filed March 27, 1914. Serial No. 827,667.

per cent. of the barium; and method II, hereinafter described, involving the precipie tation of the mixed hydroxids by addition of fixed alkali hydroxids, permits the separation of about 32 per cent. of the radium with two per cent. of the barium, or sixteen per cent. of the radium for each one per cent. of. the barium. These methods are, therefore, from five to twelvetimes as effective'as the fractional recrystallization of the chlorids.

Method I is as follows (1) The barium chlorid or other soluble barium salt, containing radium, with or without other radio active substances,-as ob-' tained by the treatment ofradium-bearing minerals, is dissolvedin Water and the hot or cold solution is mixed with an excess of a solution of sodium hydroxid or other caustic alkali, the concentrations of the solutions being sufiicient to cause the pre: cipitation of the larger part of the barium as hydroxid when the solution is cold.

(2) The barium hydroxid crystals are then separated by filtration or otherwise from the solution, which contains most of the sodium ch'lorid formed, together-with a small proportion of. the barium. The barium which remains in solution is much richer in radium than that which is deposited in the form of crystals: for example, when five per cent. of the barium is left in the solution and 95 per cent. in the crystals, the solution contains approximately 35 per cent. of the radium, and the crystals approximately 65 per cent. H

(3) The radium-bearing barium hydroxid crystals obtained according to (1) and (2) are now dissolved in hot or boiling in which they are very soluble, and the solution is cooled to normal temperature, or better to, zero centigrade. A large part ofthe barium hydroxid crystallizes out, and again there occurs a great enrichment in radium of the barium remaining in the solution.

(4) The barium hydroxid crystals are again separated and dissolved in hot water,

and the process above described isrepeat'ed as often as may be desired.

(5) The solutions containing the barium enriched in radium are further concentrated by the fractional crystallization of water,

the hydro-Kids: for this purpose the barium and radium may be precipitated, for example' as carbonates, separated from the liquid, re-dissolved as chlorids, and these chlorids converted into hydroxids and fractionally concentrated as above described.

Or the enriched hydroxid solutions may be suitably concentrated by evaporation, and the barium hydroxid again allowed to crystallize from the cold concentrated solutions 1 droxid and containing also radium or otherradio-active substances, presumably also ,as

hydroxids,'I add a sufiicient amount of a strong solution of sodium hydroxid' or potassium 'hydroxid (for .exa'mplefathirty-per cent. solution of sodium hydroxid) to cause' the precipitation of. the larger part of the barium hydroxid still remaining in the solution. By'. this means a larger proportion of the barium than of the radium is precipitated, so that the remaining solution isnow much richer in radium than before the treatment with the sodium or potassium hydroxid solution.

An illustrative example of the practice .of

the above-described'method is as follows :1

41 grams of barium chlorid containing 118 units (arbitrary) of mesothorium one were dissolvedin 180 cc. of water, and treated with 75 cc. of a thirty per cent. solution of I caustic soda free from carbonate, this 001'- responding approximately to a fifty per The solution 'was cooled to zero degrees centigrade and cent. excess of caustic soda.

.the crystals of barium hydroxid filtered out. 'The filtrate yielded 1.53 grams of BaCl .2H O. The crystals were dissolved in 180 cc. of hot water, cooled to zero, and.

20 cc. of thirty per cent. caustic soda was added. The mixture was permitted to stand at zero degrees centigrade for fifteen minutes, and was then filtered. The process was repeated until a total of six filtrates had been obtained. The amount of barium and .also of mesothorium-one in each filtrate, as well as in the residualbarium hydroxid crystals, was accurately determined with the following results Weight of Arbitrary units of No. of filtrate. BaC1z.2H=O in each mesotnorium-one filtrate. in each filtrate.

Grams. 1 1.53 22. A 1. 10 13. 2 8 84 8. 8 4 67 7.0 5 .84 4. 6 6 5S 2. 3

-The residue of barium hydroxidcrystals was found to contain 88 per cent. of the original barium and six per cent. of the original mesothorium-one.v

By the above-described methods, I have concentrated radium, mesothorium-one and thorium-X, singly and also collectively, from mixtures co taining much barium, with rapidity and ease,

, It is desirable that the method be carried 'out with exclusion of :air, on account of the tendency to the formation of barium carbcnate by the action of the carbon dioxid of the airbut this'is not regarded as es- ?sential to the invention. 7 Y

I claim 1. The method of separating and concern tr'at-ing radio-active substances, such as radium, mesothorium-one and thorium-X, from bar1um compounds, which comprlses convertingfthe barium compounds and radio-active substancesinto hydroxids, and

fractionally separating the barium hydroxid fromthe solution.

-2. In a method of separating and concentrating radio-active substances, such as radium, mesothorium-onej; and thorium-X, from barium compounds, the step which consists in partially precipitating the hy-' droxids of barium and the radio-active sub- 10o stances from solution.

3. In a method of separating and concentrating radio-active substances, such as radium, mesothorium-one. and thorium-X,

from barium compounds, the step which consists in partially precipitating the hydroxids of barium and the radio-active substances from solutionby the addition of alkali-metal hydr'oxids.

In testimony whereof I aflix my signa ture in presence oftwo witnesses.

p I HERBERT N. MCCOY. Witnesses:

Orro N. BERNDI, V R E G. MoCoY. 

